Method of forming sulphonic acid chlorides of couplers



Patented M9330, 1944 METHOD OF FORG: SULPHONIC ACID CHLOES F DUKIPLERS Henry Dudley Porter and Arnold Weissberger,

Rochester, N. 3., assignors to Eastman Kodak @ompany, Rochester,

New Jersey N. Y., a corporation of No Drawing. application September 26, will Serial No. 35$,494. in Great Britain .lanuary3,

ii Claims. ((31. 260-346) This invention relates to a method of preparing intermediates used for the production of color forming compounds for color photography.

It is known that colored photographic images may be formed by using a developer which forms a colored compound on development, and that the colored compound thus formed is deposited adjacent to the silver grains of the silver-image during the development. It is also known that a colored image may be formed by adding to certaln developer solutions or by incorporating in the gelatino-sllver-halide emulsion before or after exposure, a compound which couples during development with the oxidation product .of the developing agent and forms a coloring substance which is likewise deposited adjacent to the silver grains of the silver image during development. Such a compound, which is employed in conjunction with a developing agent for the silver and which couples with the oxidation product thereof,

during development, is referred to herein as a coupling component or coupler.

fioupling components are reacted with the developmeht product of primary aromatic amino developing agents by reason of a coupling function which is a functional or reactive group common to these compounds. This reactive group takes the form oi a reactive methylene or reactive ethenol group. A reactive methylene group is a CH2 group which is reactive in the coupling process. The CH2 group is usually presout between two negative centers as in the groups the hydrogen atoms of the methylene group may, in general, be substituted without destroying the chemical activity of the group. A reactive ethenol group is the group as in the phenolic and naphtholic coupler compounds which are presumably active in the ortho or para position with respect to the position of molecule of the coupler is non-diffusing in the emulsion. Non-diffusing couplers may be-made by reacting the sulphonic acid chlorides with high molecular substances containing amino or hydroxyl groups, such as gelatin, cellulose, and synthetic resins such as polyaminostyrene, polyh'ydroxystyrene and polyvinyl alcohol. The preparation of sulphonic acid chlorides of aromatic compounds by reaction of the aromatic compound with chlorosulphonic acid is well known (Smiles 8; Stewart Organic Syntheses collective vol. I, page 8 (1932), published by John Wiley 8: Son) However, the sulphonyl chlorides of couplers have not been prepared by this or any other'method. The references in the literature (Chem. Abst. 23, 3205 (1929), Chem. Abst. 24, 4508 (1931), German Patent 685,361, 1939) to the reaction of chlorosulphonic acid with active methylene compounds, show that the methylene group has been substituted, which is not the case in the present invention.

It is, therefore, an object of the present invention to provide a method for reacting chlorosulphonic acid with compounds containing a reactive methylene group. A further object is to provide novel coupler intermediates for color photography. Other objects will appear from 'the following description of our invention.

These objects are accomplished by reacting an aromatic compound containing a reactive methylene group with chlorosulphonic acid at low temperature and limiting the time of reaction to the order of a few days.

The couplers which may be treated according to our invention include acyl-acetanilides such as aceto-acetanilide, benzoyl-acetanilide and anisoyl-acetanilide, cyano-acetyl compounds, such as cyano-acetyl-naphthalene, cyano-acetyl-coumarone, etc. These compounds are treated with an excess of chlorosulphonic acid while keeping the temperature of the reaction mixture below about 10 C. The reaction time is limited, the

reaction being allowed to proceed for about a day or two. The reaction is then terminated and ,it is found that this procedure introduces a sulphonyl chloride group into the aromatic ring portion of'the molecule without afiecting the reactive methylene group.

The following examples, which are illustrative only, indicate the 'method of forming sulphonic acid chlorides of typical couplers according to our method.

EXAMPLE 1.-2 cyanoacetylnaphthaZene-:rsulphonyl chloride In a 3--liter, three-necked flask, fitted with an efiicient mechanical stirrer and a thermometer,

When all the coupler has been added, the mixture is stirred at -15 for 1-2 hours and is then left standing at room temperature for 60-65 hours, the flask being protected during this time by means of a calcium chloride tube. The excess acid is then decomposed by running the solution in a rapid stream from a dropping funnel, with vigorous mechanical stirring, into a mixture or 19 kg. of crushed ice and 1 liter of concentrated hydrochloric acid. After it has stood for 10-15 minutes, the light-yellow acid liquor is decanted from the crude sulfonyl chloride, which forms a single sticky mass on the bottom of the flask.

- It should not be attempted to'collect the solid liter portions of cold water, after which a sample washing should no longer be acid to Congo red. After drying over anhydrous magnesium sulphate, the chloroform is distilledoif under reduced pressure (.20 mm. or less), heating the distilling flask in a water bath at 40".

eflicient mechanical stirrer and a thermometer, is placed 1250 cc. (about 19 moles) of chlorosulphonic acid. The flask is cooled in an ice-salt freezing mixture to about l.0 0., and to the Under these conditions, the temperature inside the flask is below room temperaturefland very little decomposition will occur. The sticky residue is worked with 200 cc. of ethyl acetate until it becomes granular, is filtered ofi', and washed with ether until it is no longer stick'y; about 1 liter in 200-cc. portions is required.

The sulphonyl chloride forms a yellow powder, M. P. 115-117. Yield 470 g. (62.6%.)

ExAMrLs 2. 2 cyanoacetylcoumarone 5 phonyl chloride sult CH C1028 C I a y In a 3-liter, three-necked flask, fitted with an cold acid, in small portions with vigorous stirring, is added 500 g. (2.7 moles) of purified Z-cyanoacetylcoumarone. The rate of addition should be such that the temperature does not rise above +5 0.; about 30 minutes is required. When all the coupler has been added, the mixture is stirred at 0 for 2 hours and then at room temperature overnight, or for about 15 hours.

At the end of this time, the excess chlorosulphonic acid is decomposed by pouring the mixture with vigorous stirring onto 10 kg. of crushed ice, introducing the mixture simultaneously from two l-liter dropping funnels. About 10 minutes is required for the decomposition. After being allowed to settle for a few minutes, the sulphonyl chloride is filteredofi onto flannel, using two 12- inch Buchner funnels. The two cakes are combined, stirred with about 5- liters of ice-water, and again filtered oil on a large funnel. The cake is again broken up, and stirred this time with an ice-cold solution of 500 g. of sodium acetate in 5 liters of water. Any lumps should be broken up as thoroughly as possible with a stick. The sulphonyl chloride is finally filtered off, washed on the funnel with about 5 liters of ice-water, and sucked dry. The final washings should not be acid to Congo red.

The cake, sucked as free as possible from water, is broken up and dissolved in 3 liters of ethyl acetate. The ethyl acetate solution is dried over anhydrous magnesium sulphate and the ethyl acetate is distilled off under reduced pressure (40-50 mm. Hg), the distilling flask being heated in a water bath which has a temperature no higher than 60. Toward the end of the concentration the temperature should be as low as 20. The inside temperature should never rise above 20. The residue is stirred with 500 cc. of benzene, is filtered ofl, and washed on the filter with about 1 liter of ether. This washing removes a small amount of tarry impurity, which tends to make the product sticky, and leaves the sulphonyl chloride as a light-yellow powder which appears to be quite stable. The melting point otsthe pure material is 134-135", but the product obtained fromany particular run may melt'as much as 10 lower and still be entirely satisfactory. In most cases the melting point Was 130-432.

The yield is about 250 g. (33%).

EXAMPLE 3.-p-(w-Benzoylacetamino) benzenesulphony! chloride To 10kg. (large excess) of chlorosulphonic,

acid cooled to 0-5 in an ice salt bath is added in small increments 2 kg. (8.35 moles) of benzoylacetanilide, while stirring vigorously. The temwith soc cc. of ether.

oeroture is kept below or by the occasional ed dltiori of dry ice. After all is added the ice both is removed and the mixture stirred at room temperature for i hours. The reaction mixture isdecorri 'iosed by adding in a, thin stream to a,

vigorously stirred mixture of ice (o. convenient 1 amount for stirring in the receptacle used) and concentrated hydrochloric acid. Ice

storiding, the product iloets to the top with the ether, and the bulk or the water solution may be drawn ofi. The product is their auction ill tered, washed with 1 liter oi water and them After being sucked as dry as. possible it is dried at room temperature for to hours, grinding it when possible. The prodnot is then purified by extracting with hermetic 2o l. in all) from which it crystallizes on ccol-= ling, otter filtering the hot solution. Yield 13%- lfillo g.'(46.5-53.5%). M. P. lit-150 As stated oloove, these sul ollonic acid chlorides ol couplers may he rewted with chimes to form sulphoriemines or with alcohols or compods containing o hydroxyl group to io esters. fiulphohcmides which may he formed in this troy ore described in 'iiittum, Peterson. and Porter U. S. Potent 2,211,238, granted January 2?, role,

and sulphonic esters are, described in Peterson U. Potent 2,289.80 l, granted July M, 19 252. mphohlc ester couplers formed'lrom sulphohrl chlorides or couplers are described in our U. S.

Potent 2,289,805, rooted d it, 1942.

it is to he understood thet the examples cool reoctiori conditions described herein are illiistro I this only end that our invention is to he token as limited only by the scope of the appended clolms.

We claim:

, l. The ethod of producing o sulphonic acid chloride or on aromatic compound cootoihioo o up selected from the close cohsisti of .jro

o and fitlwi-lw-Clil, which comprises adding soidoromotio oomood slowly and in smell portions to on excess or chloro sulphooic acid at c temperoture not substantigilly above it) C. and limiting the period or re. action to a time of a. few days, to introduce a Mia sulphonyl chloride group into only the aromatic ring portion of sold compound.

2. The method of producing o sulphonic acid chloride or o, hemoyloceteo-benzene which comprises adding sold ecetomino-oenzene slowly and in smell portionsto on excess of chlorosulphonic acid at a. temperature not substantially above 10 C. and limiting the period of reaction to a time or o few days, to introduce o culphon'yl chloride group into only the benzehelrinz por tion of sold ocet o-loeiosene.

3. The method cl producing o sulphonic acid chloride of o-(o-lienzoylscetomino) benzene which comprises adding soidecetcmino-benzerie slowly end in small portions to an excess of chlcrosulphoriic cold at o temperature hot substoiitiallyobove 10 C. and limiting the period of reaction to o time of e few lilo-rs, to introduce o siilphonyl chloride group into only the benzene rim; portion of sold acetominohenzene. I

o. The method of producing c sulploonic acid chloride of on organic compound containing a. cyorioocetyl group and on aromatic ring portion which comprises adding said organic compound slowly and in smell portions to an excess of chlorosulphorilc acid at o temperature not substantially shove 10 (2. and limiting the period or reaction to a time or o ifew days, to introduce o sulphonyl chloride group into only the eromotic ring portion of said organic compound.

5. The method of producing a sulphonic acid chloride of o z-cyonoacetyl-coumorone which comprises adding a, Z-oyenoecetyl-coumarone slowly and in small portions to an excess of chlorosulphoriic cold ct o temperature not sub stantially alcove 10 C. end limiting the period of reaction to at time of 9. low deys, to introduce o, sulphonyl chloride group into only the aromatic ring portion of sold Z-cyonoocetyl-coumarrine.

o. The method of producing or sulphonic acid chloride or o 2-cycnoocetyl-nophtholene which comprises eddlrie sold Z-cyonoacetirl hophtha-' motic ring portion of said 2-cyanoocetylnophthelone. so

rr DUDLEY PORIER. mom WEISSBERGER. 

